Process for producing dichloroacetoxypropane and derivatives thereof

ABSTRACT

A process for producing dichloroacetoxypropane comprising reacting allyl acetate with chlorine in a gaseous phase in the presence of a catalyst comprising an element of Group 16 of the long-form Periodic Table or in the absence of a catalyst. The dichloroacetoxypropane obtained may be converted to dichloropropanol and epichlorohydrin.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.09/249,781, filed Feb. 16, 1999, now U.S. Pat. No. 6,118,030 and claimsbenefit of Provisional App. Ser. No. 60/082,625 filed Apr. 22, 1998.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for the production ofdichloroacetoxypropane and derivatives thereof which are raw materialsfor useful organic products.

2. Description of the Related Art

The term “dichloroacetoxypropane” as used herein refers to2,3-dichloro-1-acetoxypropane, 1,3-dichloro-2-acetoxypropane or amixture thereof. Further, the term “dichloropropanol”, as used hereinrefers to 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol or a mixturethereof.

A process for producing dichloroacetoxypropane by reacting allyl acetatewith chlorine in a liquid phase is described, for example, in Khim.Prom., No. 5, 277-280 (1981), Khim. Prom., No. 6, 328-335 (1982) andJapanese Examined Patent Publication (Kokoku) No. 52-16091. The reactionis represented by the following formula.

These conventional techniques all relate to the reaction in a liquidphase and use a metal salt such as a metal halide as a catalyst.However, when a metal salt is used as a catalyst, the catalyst must beseparated and recovered after the reaction. Moreover, the metal saltdissolves into the reaction solution and the separation and recovery ofthe dissolved metal salt presents another problem. In order to preventthe metal salt dissolving, Japanese Examined Patent Publication No.52-16091 proposes a supported catalyst in which a metal salt issupported on a support. However, it is still difficult to prevent themetal salt dissolving out of the support.

Furthermore, in all the above-described conventional techniques, thereaction of allyl acetate with chlorine is effected in the presence ofan organic solvent. The use of an organic solvent has, however, aproblem in that a recovery step therefor is necessary or loss of theorganic solvent is caused at the time of recovery.

There is still another problem in that since the production ofdichloroacetoxypropane by the reaction of allyl acetate with chlorine isan exothermic reaction, external cooling or the like is necessary inorder to obtain dichloroacetoxypropane with high efficiency and thiscauses a loss of energy.

As a conventional technique for chlorination in a gaseous phase, areaction of ethylene with chlorine is known (see, for example, U.S. Pat.No. 2,099,231). However, a method of producing dichloroacetoxypropane byreacting allyl acetate with chlorine in a gaseous phase has not hithertobeen reported.

BRIEF SUMMARY OF THE INVENTION

An object of the present invention is to overcome the defects of theliquid phase processes conventionally employed for the production ofdichloroacetoxypropane, more specifically, problems such as thenecessity of a step for separating and recovering a catalyst, thenecessity of a step for recovering an organic solvent resulting from useof an organic solvent, the loss of the organic solvent during recoveryor the loss of energy accompanying external cooling, and to provide anindustrially more advantageous production process fordichloroacetoxypropane as well as an industrially more advantageousproduction process for a derivative of dichloroacetoxypropane, such asdichloropropanol or epichlorohydrin, using the above-described process.

As a result of extensive investigations to solve the above-describedproblems, the present inventors have found that the object of thepresent invention can be attained by a process for producingdichloroacetoxypropane, comprising reacting allyl acetate with chlorinein a gaseous phase in the presence of a catalyst comprising an elementof Group 16 of the long-form Periodic Table or in the absence of acatalyst. The present invention has been accomplished based on thisfinding. In other words, the present invention provides a process forproducing dichloroacetoxypropane, comprising reacting allyl acetate withchlorine in a gaseous phase in the presence of a catalyst comprising anelement of Group 16 of the long-form Periodic Table or in the absence ofa catalyst.

The present invention also provides a process for efficiently producingdichloroacetoxypropane by reacting allyl acetate with chlorine in agaseous phase and then efficiently producing a derivative thereof, forexample, a process for efficiently producing dichloropropanol from theresulting dichloroacetoxypropane and a process for further producingepichlorohydrin in good efficiency.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

Allyl acetate for use in the present invention may be any commerciallyor industrially available allyl acetate and is not particularly limited.

Chlorine for use in the present invention may be any commercially orindustrially available chlorine and is not particularly limited.

The catalyst for use in the production of dichloroacetoxypropaneaccording to the present invention is a catalyst containing an elementof Group 16 of the long-form Periodic Table, preferably Te. The elementmay be in the form of a compound containing the element.

Specific examples of the compound include halides, oxides, carbonates,phosphates, nitrates, sulfates, oxyhalides, basic carbonates,hydroxides, carboxylates and organic metal complexes of theabove-described elements, however, the present invention is by no meanslimited thereto. Of these, halides and oxides are preferred.

Examples of the halogen of the halides or oxyhalides include fluorine,chlorine, bromine and iodine. Of these, chlorine is preferred.

The catalyst can be used in any known form and is not particularlylimited. The catalyst is preferably a support type, a coprecipitationtype or an ion exchange type, more preferably a support type.

The element of Group 16 of the long-form Periodic Table to be used forthe catalyst in the present invention may suitably have a concentrationof from 0.01 to 100 wt %, preferably from 0.1 to 50 wt %, based on thetotal weight of the catalyst.

In the case of a supported catalyst, specific examples of the supportinclude single oxides such as alumina, zirconia, titania, niobia, silicaand magnesia, complex oxides such as silica alumina, and zeolite,heteropolyacids, activated carbon and polymers, but the support is notparticularly limited thereto.

The supported catalyst can be prepared by a known process, for example,a process for impregnating a metal compound into a support. Morespecifically, for supporting a metal compound on a support, the metalcompound is dissolved in an appropriate solvent such as water, alcohol,hydrochloric acid or aqueous ammonia, in an amount such that the supportcan absorb the solution. To the resulting solution, a support having anappropriate particle size is added and, after being impregnated with thesolution, the support is dried. The drying may be performed either undernormal pressure or a reduced pressure. For example, in the case ofdrying the catalyst under a reduced pressure, the drying may beperformed in a vacuum dryer at from 20 to 300° C. The drying ispreferably continued until the catalyst reaches a constant weight.

The dried supported catalyst may be used as it is in the reaction or maybe calcined before use. The calcination may be performed in anatmosphere of nitrogen, carbon dioxide, air, oxygen, hydrogen or thelike, however, the atmosphere is not particularly limited as far as itmatches the purpose.

The catalyst containing an element of Group 16 of the long-form PeriodicTable may be prepared by any known process. For example, the catalystmay be prepared by calcining and reducing a catalyst containing anelement of Group 16 of the long-form Periodic Table in an atmospherecontaining a reducing agent such as hydrogen, paraffin or olefin,however, the present invention is by no means limited thereto.

The calcination temperature is not particularly limited, however, it ispreferably a temperature higher than the reaction temperature. Thecalcination time is also not particularly limited, but the calcinationis preferably continued until the catalyst reaches a constant weight.

The catalyst used in the present invention may have any shape such as atablet, a ring, a sphere, a micro-sphere or an extrusion but is notparticularly limited. The molding may be performed by any known methodsuch as compression molding, extrusion molding or spray dryinggranulation. Furthermore, the catalyst may be used after being blendedwith an inactive filler.

As the filler, there may be mentioned an inactive solid material such asglass beads, silicon carbide or silicon nitride, but is not limitedthereto.

When the reaction is performed according to the invention, even if theexternal temperature is constant, the temperature of the reactionmixture may locally be raised by local heat generation due to, forexample, the process of the reaction at a certain zone of the catalystlayer. As a result, there may be caused problems such as the increase ofby-products and reduction of catalyst life. In such a case, the localheat generation may be inhibited by blending and diluting the catalystwith the above-mentioned filler.

The blending of the catalyst with the filler may be carried out by anyknown method, such as a method of uniformly blending or a method ofvarying the blending ratio of the catalyst and the filler with respectto the flowing direction of the reaction gas mixture, but is not limitedthereto.

The filler may have any shape such as a tablet, a ring, a sphere, amicrosphere or an extrusion, but is not limited thereto. The shape maybe the same as or different from that of the catalyst.

In the present invention, a condition such that dichloroacetoxypropane(e.g., 2,3-dichloro-1-acetoxypropane (boiling point: 191 to 192°C./100.7 kPa) and/or, 1,3-dichloro-2-acetoxypropane (boiling point: 195°C./101.3 kPa)) is in the gaseous state is preferred for the gaseousphase reaction to proceed smoothly. From the point of view of thereaction result, lowering of the reaction heat, separation of thereaction product from raw materials after the reaction and executionform, a diluent is preferably added.

The diluent is not particularly limited as far as it does not inhibitthe production of dichloroacetoxypropane, but an inert gas is suitablyused. The inert gas is not particularly limited and examples of theinert gas which can be used include nitrogen, carbon dioxide, helium andargon, however, the present invention is not limited thereto by anymeans. Of those mentioned, nitrogen is preferred.

With respect to the raw material gas for use in the production ofdichloroacetoxypropane, the composition may be selected from the rangesuch that allyl acetate is from 0.01 to 99.99 mol %, chlorine is from0.0001 to 60 mol % and the diluent is from 0 to 99.99 mol %.

For achieving smooth gaseous phase reaction, the above-describedcomposition of the raw material gas is preferably selected so thatdichloroacetoxypropane produced can be kept in a gaseous state. Morespecifically, the composition of the raw material gas is preferablyselected such that the partial pressure of dichloroacetoxypropaneproduced becomes lower than the saturated vapor pressure ofdichloroacetoxypropane at the reaction temperature.

The molar ratio of chlorine to allyl acetate (chlorine/allyl acetate)may suitably be from 0.001 to 1.5, preferably from 0.01 to 1.0. If themolar ratio of chlorine/allyl acetate exceeds 1.5, a side reaction suchas substitution may occur with the excess chlorine or recovery of alarge amount of unreacted chlorine may be disadvantageously needed,whereas if the molar ratio of chlorine/allyl acetate is less than 0.001,there may arise a problem in that a large amount of allyl acetate mustbe recovered.

In the present invention, the molar ratio of the diluent to the chlorine(diluent/chlorine) may suitably be from 0 to 2,000, preferably from 0 to1,000, however, the present invention is by no means limited thereto.

The raw material gas may suitably have a space velocity of from 100 to12,000 hr⁻¹, preferably from 300 to 8,000 hr⁻¹, however, the presentinvention is by no means limited thereto.

In the process of the present invention, the reaction temperature at thetime of producing dichloroacetoxypropane may suitably be from 70 to 300°C., preferably from 80 to 250° C. If the reaction temperature exceeds300° C., there may arise a problem such as increase of the reactionproduct by substitution with chlorine or reduction of the catalyst lifedue to by-production or accumulation of a high boiling point compound,whereas if the reaction temperature is lower than 70° C., there mayarise a problem in that a large amount of diluent resulting fromincrease of the amount of the diluent used for maintaining the gaseousphase state must be recycled, the productivity decreases or reaction ina stable gaseous phase becomes difficult.

The heat generated as the reaction proceeds between allyl acetate andchlorine may be discharged from the system by warm water or heatingmedium, so that the reaction temperature can be maintained in a constantrange. In this case, it is possible and useful to use the heat taken outby warm water or a heating medium as a heat source of other facilities.

The pressure at the time of producing dichloroacetoxypropane accordingto the process of the present invention may suitably be from 10 to 1,000kPa, preferably from 50 to 500 kPa. If the reaction pressure is eitherlower than 10 kPa or higher than 1,000 kPa, the practice becomesindustrially difficult and this is not preferred.

In practicing the present invention, the reaction system for the gaseousphase reaction of allyl acetate with chlorine may be any known systemand is not particularly limited, however, a continuous flow system ispreferred.

The form of the reaction vessel for use in the present invention is notparticularly limited, however, a fixed bed reaction vessel or afluidized bed reaction vessel is preferred.

In the present invention, the raw material gas may be introduced into areaction vessel by any known method and the method is not particularlylimited. For example, a method of introducing allyl acetate afterpreviously vaporizing it may be used. Chlorine may be introduced by anymethod such as a method of introducing chlorine into a reaction vesselafter previously combining it with allyl acetate or a method ofseparately introducing these members into a reaction vessel. A method ofintroducing allyl acetate and chlorine such that these can efficientlycontact on a catalyst, for example, a method of previously mixing allylacetate and chlorine in a static mixer (see, Kagaku Sochi(ChemicalApparatus). May, 74-78 (1994)) and then introducing these into acatalyst, may be used, however, the present invention is by no meanslimited thereto.

The manner of adding the diluent for use in the present invention is notparticularly limited and any known form may be used, for example, thediluent may be added to allyl acetate, may be added only to chlorine ormay be added to both of allyl acetate and chlorine.

For collecting dichloroacetoxypropane from the gas containingdichloroacetoxypropane produced in the above-described reaction vessel,any known method may be used. For example, by cooling the outlet of thereaction vessel, the gas component and the liquid component containingdichloroacetoxypropane as a product can be separated from each other andby distilling and purifying this liquid component containingdichloroacetoxypropane, dichloroacetoxypropane can be obtained.

In the case of using an inert gas as the diluent, the inert gas afterseparating dichloroacetoxypropane therefrom may be re-used bycirculating it as it is or after purification. When allyl acetate isused in excess to chlorine, unreacted allyl acetate may be contained inthe liquid component depending on the cooling temperature, but this canbe re-used after separating it from dichloroacetoxypropane bydistillation. Also, after concentrating only the objectivedichloroacetoxypropane by setting the cooling temperature at a highertemperature, the unreacted allyl acetate in the gaseous state can bere-used by circulating it as it is or after purification.

Dichloroacetoxypropane produced by the process of the present inventionmay be a mixture of 2,3-dichloro-1-acetoxypropane and1,3-dichloro-2-acetoxypropane. The dichloroacetoxypropane produced mayhave a compositional ratio in mol % such that2,3-dichloro-1-acetoxypropane is from 5 to 100 mol % and1,3-dichloro-1-acetoxypropane is from 0 to 95 mol %. These two isomerscan be separated by a known method or can be separated by distillationor the like, however, the separation method is not limited thereto.

Depending on the use of dichloroacetoxypropane, for example, when it isused for the production of a derivative thereof such as dichloropropanolor epichlorohydrin, the dichloroacetoxypropane obtained by theabove-described reaction can be used as a starting material for the nextstep without separating these two isomers.

A production process of dichloropropanol or epichlorohydrin using thedichloroacetoxypropane produced by the present invention is describedbelow. Dichloropropanol and epichlorohydrin are compounds useful as araw material for producing various compounds, as a solvent, as astarting material of epoxy resin or synthetic rubber, or as a stabilizerof chlorinated rubber.

The production process of dichloropropanol comprises the following firstand second steps and the production process of epichlorohydrin comprisesthe following first to third steps.

First step:

A step of reacting allyl acetate with chlorine in a gaseous phase in thepresence of a catalyst comprising an element of Group 16 of thelong-form Periodic Table or in the absence of a catalyst to producedichloroacetoxypropane.

Second step:

A step of subjecting the dichloroacetoxypropane obtained in the firststep to hydrolysis or alcoholysis to produce dichloropropanol.

Third step:

A step of dehydrochlorinating the dichloropropanol obtained in thesecond step to produce epichlorohydrin.

The first step is described in detail above in connection with theproduction method of dichloroacetoxypropane. The second and third stepsare described in detail below.

The second step is a step of subjecting the dichloroacetoxypropaneobtained according to the present invention to hydrolysis or alcoholysisto produce dichloropropanol.

The hydrolysis or alcoholysis of dichloroacetoxypropane can be performedby a known method and the method is not particularly limited. Forexample, the method described in Khim. Prom., No. 6, 328-335 (1982) maybe preferably used, where dichloroacetoxypropane is hydrolyzed oralcoholyzed using an acid catalyst such as hydrochloric acid, sulfuricacid or a cation exchange resin, to produce dichloropropanol.

In the case of hydrolysis, the molar ratio of water todichloroacetoxypropane (water/dichloroacetoxypropane) may suitably befrom 0.5 to 20.0, preferably from 1.0 to 10.0.

In the case of alcoholysis, the molar ratio of alcohol todichloroacetoxypropane (alcohol/dichloroacetoxypropane) may suitably befrom 0.5 to 20, preferably from 1.0 to 10.

Examples of the alcohol used for alcoholysis include methanol, ethanol,n-propanol, isopropanol, n-butanol, isobutanol, t-butanol and allylalcohol, however, the present invention is by no means limited thereto.More preferred is allyl alcohol.

When allyl alcohol is used for the alcoholysis, allyl acetate isproduced along with dichloropropapnol. This dichloropropanol can beconverted to epichlorohydrin at the third step. On the other hand, allylacetate can be recycled to the first step to be used as a raw materialfor dichloroacetoxypropane. When an alcohol other than allyl alcohol isused for the alcoholysis, there may arise a problem such as of thesupply and demand balance of dichloropropanol or epichlorohydrin withthe concurrently produced acetate ester. For example, when butanol isused, there may arise a problem such as of the supply and demand balanceof dichloropropanol or epichlorohydrin with butyl acetate, but theproblem may be prevented when using allyl alcohol.

Allyl alcohol used for the alcoholysis according to the presentinvention may be either anhydrous or hydrous allyl alcohol. In the caseof the alcoholysis by hydrous allyl alcohol, the produced allyl acetateforms some azeotropic components with unreacted allyl alcohol and water.Furthermore, dichloroacetoxypropane is hydrolyzed with water containedin hydrous allyl alcohol to produce acetic acid. It is possible toseparate allyl acetate, unreacted allyl alcohol, water and acetic acid,as a low boiling point component in the reaction system, fromdichloropropanol and unreacted dichloroacetoxypropane. Then, allylacetate, hydrous allyl alcohol and acetic acid can be separated from thelow boiling point component and purified by any known method. Forexample, the separation and purification may be effected according tothe distillation and two-phase separation described in Japanese ExaminedPatent Publication (Kokoku) No. 1-20137. The separated and purifiedallyl acetate may be recycled to the first step, and hydrous allylalcohol and acetic acid may be recycled to the second step.

The reaction temperature in the second step is not particularly limitedand it is preferably from 40 to 200° C., more preferably from 60 to 180°C.

The reaction in the second step may be performed in any known system,and specific examples of preferred reaction systems include a batchsystem, a semi-continuous system and a continuous system, however, thepresent invention is by no means limited thereto.

Dichloropropanol produced in the second step can be separated andpurified by any known method. For example, the dichloropropanol ispreferably separated and purified by distillation in the same manner asin the method described in Japanese Examined Patent Publication (Kokoku)No. 7-25711, however, the present invention is by no means limitedthereto.

The third step is a step of dehydrochlorinating the dichloropropanolobtained in the second step to produce epichlorohydrin.

The third step can be performed by any known method. For example,epichlorohydrin is preferably produced by reacting dichloropropanol withan aqueous alkali solution or alkali suspension in the same manner as inthe method described in Japanese Unexamined Patent Publication (Kokai)No. 60-258172, however, the present invention is by no means limitedthereto.

The alkaline compound used in the third step is not particularlylimited. Examples thereof include an aqueous solution and suspension ofcalcium hydroxide, sodium hydroxide, potassium hydroxide, sodiumcarbonate or potassium carbonate, however, the present invention is byno means limited thereto.

The amount of the alkaline compound used is not particularly limited,however, the alkaline compound is preferably used in an amount of from1.0 to 1.5 equivalent, more preferably from 1.03 to 1.3 equivalent, per1 mol of dichloropropanol.

The reaction of the third step may be performed by any known method. Forexample, the reaction is preferably performed by:

(1) a method of supplying an aqueous alkali solution or alkalisuspension of the raw material of dichloropropanol from the top of aplate distillation column and blowing steam from the bottom to stripepichlorohydrin produced by the reaction while subjecting to azeotropicdistillation (boiling point: 88° C.) with water; in this method, aninert gas such as nitrogen may be accompanied in addition to steam toincrease the stripping effect;

(2) a method of mixing dichloropropanol or an aqueous solution thereofwith an aqueous alkali solution or alkali suspension in a liquid phaseand reacting the mixture while stirring; or

(3) a method of allowing an inactive solvent substantially insoluble inwater to be present together and performing reaction while extractingepichlorohydrin produced into the solvent.

The methods (2) and (3) may be performed either in a batch system orcontinuous system. In the case of a continuous system, a mixingtank-type reaction, a flow-type reaction in a tower reaction vessel orthe like may be used. In the case of a flow-type reaction in a towerreaction vessel, dichloropropanol or a solution thereof and an aqueousalkali solution or alkali suspension may flow concurrently orcountercurrently while coming into contact, to thereby effect reaction.The reaction methods (2) and (3) may be combined, for example, so thatone method is used until the reaction proceeds to a certain level andthen the other method is used to allow the reaction to proceed further.

The amount of steam used for stripping epichlorohydrin produced in thethird step may suitably be such that the overhead product compositionhas a ratio by weight of water/epichlorohydrin of from 0.5 to 3.5,preferably from 1.0 to 2.5. As the amount of steam becomes larger, theselectivity of epichlorohydrin increases, however, if it is too large,high steam consumption may result. Accordingly, the amount used inpractice is limited. On the other hand, if the amount of steam is toosmall, the stripping effect may decrease and the selectivity ofepichlorohydrin may be reduced.

The reaction temperature in the third step is not particularly limitedbut it is preferably from 40 to 110° C., more preferably from 60 to 100°C. As the reaction temperature becomes lower, the selectivity ofepichlorohydrin elevates, however, since the reaction rate may decrease,the reaction time may be prolonged. The reaction pressure in the thirdstep is not particularly limited but it is preferably from 10 to 200kPa.

The present invention is described in greater detail below by referringto the Examples and Comparative Examples, however, the present inventionis by no means limited to these Examples.

Catalyst Preparation Process 1

2.25 g of a compound was dissolved or suspended in 18 g of methanol and42.75 g of a support was added to be impregnated with the liquid at roomtemperature for 30 minutes. Thereafter, the impregnated matter was airdried at 30° C. for 3 hours. The dried matter was calcined at 200° C.for 3 hours in a nitrogen stream to obtain a catalyst as a compound (5wt %)/support (95 wt %).

Catalyst Preparation Process 2

2.25 g of compound A and, based on 2.25 g of compound A, 1 moleequivalent of compound B were dissolved or suspended in 18 g of methanoland 42.75 g of a support was added to be impregnated with the liquid atroom temperature for 30 minutes. Thereafter, the impregnated matter wasair dried at 30° C. for 3 hours. The dried matter was calcined at 200°C. for 3 hours in a nitrogen stream to obtain a catalyst as compoundA+compound B/support.

Catalyst Preparation Process 3

2.25 g of compound A and, based on 2.25 g of compound A, 1 moleequivalent of compound B and 0.5 mole equivalent of compound C weredissolved or suspended in 18 g of methanol and 42.75 g of a support wasadded to be impregnated with the liquid at room temperature for 30minutes. Thereafter, the impregnated matter was air dried at 30° C. for3 hours. The dried matter was calcined at 200° C. for 3 hours in anitrogen stream to obtain a catalyst as compound A +compound B+compoundC/support.

EXAMPLE 1

Using TeCl₄ as the compound and Al₂O₃ (particle size: 1.6 mm) as thesupport, a catalyst was prepared by the catalyst preparation process 1.

16 ml of the catalyst was filled in an upright glass-made reactionvessel having an inner diameter of 14 mm and a length of 15 cm andequipped with glass tubing for the measurement of temperature.

The reaction vessel was heated to 140° C. with a heating medium toadjust the pressure to 101 kPa. Then, a raw material gas comprising 1.3mol % of chlorine, 3.3 mol % of allyl acetate and 95.4 mol % of nitrogenwas introduced into the reaction vessel at a space velocity of 4,131 h⁻¹and reacted. The allyl acetate was previously vaporized through avaporizer set at 140° C.

Thereafter, the outlet of reaction vessel was cooled, and the distillatecondensed by the cooling was collected. The distillate obtained wasanalyzed by gas chromatography to determine the yield ofdichloroacetoxypropane (based on the raw material chlorine) and thecompositional ratio (mol %) thereof. The measurement was performed usingthe maximum temperature of the catalyst layer in the reaction vessel asthe reaction temperature. The results obtained are shown in Table 1. Inthe table, DCAP represents dichloroacetoxypropane, 2,3-compoundrepresents 2,3-dichloro-1-acetoxypropane and 1,3-compound represents1,3-dichloro-2-acetoxypropane.

EXAMPLE 2

Reaction was performed in the same manner as in Example 1 except forusing ZnCl₂ as compound A, TeCl₄ as compound B, Al₂O₃ (particle size:1.6 mm) as the support and a catalyst prepared by the catalystpreparation process 2. The results are shown in Table 1.

EXAMPLE 3

Reaction was performed in the same manner as in Example 1 except forusing ZnCl₂ as compound A, MgCl₂ as compound B, TeCl₄ as compound C,Al₂O₃ (particle size: 1.6 mm) as the support and a catalyst prepared bythe catalyst preparation process 3. The results are shown in Table 1.

EXAMPLE 4

Reaction was performed in the same manner as in Example 1 except forusing ZnCl₂ as compound A, MgCl₂ as compound B, TeCl₄ as compound C,ZrO₂ (particle size: 0.5 to 2.0 mm) as the support and a catalystprepared by the catalyst preparation process 3. The results are shown inTable 1.

TABLE 1 Reaction Compositional Ratio Example Temperature (mol %) of DCAPNo. Catalyst (wt %) (° C.) DCAP 2,3-compound 1,3-compound 1 TeCl₄(5.0)/Al₂O₃ (95.0) 155 84.5 80.3 19.7 2 ZnCl₂ (4.6) + TeCl₄ (9.0)/ 15790.2 70.4 29.6 Al₂O₃ (86.5) mole ratio Zn/Te = 1/1 3 ZnCl₂ (4.6) + MgCl₂(3.2) + 160 99.0 90.8 9.2 TeCl₄ (4.6)/Al₂O₃ (87.6) mole ratio Zn/Mg/Te =1/1/0.5 4 ZnCl₂ (4.6) + MgCl₂ (3.2) + 161 99.1 89.1 10.9 TeCl₄(4.6)/ZrO₂ (87.6) mole ratio Zn/Mg/Te = 1/1/0.5

EXAMPLE 5

Reaction was performed in the same manner as in Example 1 except forfilling a catalyst prepared according to catalyst preparation process 3by using ZnCl₂ as compound A, MgCl₂ as compound B, TeCl₄ as compound Cand Al₂O₃ (particle size: 1.6 mm) as the support in the reaction vesseland introducing a raw material gas comprising 4.8 mol % of chlorine, 5.3mol % of allyl acetate and 89.9 mol % of nitrogen into the reactionvessel at a space velocity of 1,137 h⁻¹. The results are shown in Table2.

EXAMPLE 6

Reaction was performed in the same manner as in Example 1 except foruniformly blending a catalyst prepared according to catalyst preparationprocess 3 by using ZnCl₂ as metal compound A, MgCl₂ as metal compound B,TeCl₄ as metal compound C and Al₂O₃ (particle size: 1.6 mm) as thesupport with 10.7 ml of glass beads (particle size: 0.99 to 1.4 mm) asthe filler and filling the blend in the reaction vessel and introducinga raw material gas comprising 4.8 mol % of chlorine, 5.3 mol % of allylacetate and 89.9 mol % of nitrogen into the reaction vessel at a spacevelocity of 1,137 h⁻¹. The results are shown in Table 2.

EXAMPLE 7

Reaction was performed in the same manner as in Example 6 except forusing 10.7 ml of silicon carbide (particle size: 2.0 mm) as the filler.The results are shown in Table 2.

EXAMPLE 8

Reaction was performed in the same manner as in Example 1 except forusing no catalyst. The results are shown in Table 2.

TABLE 2 Reaction Compositional Ratio Example Temperature (mol %) of DCAPNo. Catalyst (wt %) (° C.) DCAP 2,3-compound 1,3-compound 5 ZnCl₂(4.6) + MgCl₂ (3.2) + 162 98.5 89.9 10.1 TeCl₄ (4.6)/Al₂O₃ (87.6) moleratio Zn/Mg/Te = 1/1/0.5 6 ZnCl₂ (4.6) + MgCl₂ (3.2) + 159 99.1 90.3 9.7TeCl₄ (4.6)/Al₂O₃ (87.6) mole ratio Zn/Mg/Te = 1/1/0.5 7 ZnCl₂ (4.6) +MgCl₂ (3.2) + 158 99.2 90.8 9.2 TeCl₄ (4.6)/Al₂O₃ (87.6) mole ratioZn/Mg/Te = 1/1/0.5 8 None 142 21.2 95.8 4.2

EXAMPLE 9

Production of dichloropropanol: Production of dichloropropanol byhydrolysis of dichloroacetoxypropane

500 g (2.92 mol) of dichloroacetoxypropane produced in Example 5, 158 g(8.77 mol) of water and 9.3 g of a 35 wt % hydrochloric acid werecharged into a glass reaction vessel and heated at 90° C. for 5 hoursunder normal pressure. The reaction liquid obtained was distilled in adistillation column to distill the azeotropic component of water anddichloropropanol, water and acetic acid from the top and recover thebottom liquid containing dichloropropanol from the bottom. The bottomliquid obtained was further distilled to obtain 268 g (2.08 mol) ofdichloropropanol. The yield of dichloropropanol was 71.1%. Thecompositional ratio thereof was such that 2,3-dichloro-1-propanol was73.5 mol % and 1,3-dichloro-2-propanol was 26.5 mol %.

EXAMPLE 10

Production of dichloropropanol: Production of dichloropropanol byalcoholysis of dichloroacetoxypropane with n-butanol

500 g (2.92 mol) of dichloroacetoxypropane produced in Example 5, 650 g(8.77 mol) of n-butanol and 9.3 g of a 35 wt % hydrochloric acid werecharged into a glass-made reaction vessel and heated at 90° C. for 5hours under normal pressure. The reaction liquid obtained was distilledin a distillation column to obtain 343 g (2.66 mol) of dichloropropanol.The yield of dichloropropanol was 91.0%. The compositional ratio thereofwas such that 2,3-dichloro-1-propanol was 75.0 mol % and1,3-dichloro-2-propanol was 25.0 mol %.

EXAMPLE 11

Production of dichloropropanol: Production of dichloropropanol byalcoholysis of dichloroacetoxypropane with 70 wt % aqueous allyl alcoholsolution 75.0 g of dichloroacetoxypropane produced in Example 5, 50.9 gof allyl alcohol (commercial product) and 21.8 g of water (representinga 70 wt % aqueous allyl alcohol solution and an allylalcohol/dichloroacetoxypropane mole ratio of 2.0), and 1.39 g of a 35 wt% hydrochloric acid as a catalyst were charged into a glass flaskequipped with a Dimroth condenser, heated to 105° C. while stirring, andreacted under reflux for 3 hours. The reaction liquid was analyzed bygas chromatography. The product had a composition of 5.3 g of unreacteddichloroacetoxypropane, 52.3 g of produced dichloropropanol, 24.2 g ofproduced allyl acetate, 35.7 g of unreacted allyl alcohol and 22.8 g ofwater. Furthermore, it was found that 7.0 g of acetic acid was producedby the hydrolysis of allyl acetate. From the results, it was found thatthe conversion of dichloroacetoxypropane was 92.9%, the yield ofdichloropropanol was 92.5% and the selectivity of thereof was 99.5% (onthe basis of the raw material of dichloroacetoxypropane), and the yieldof allyl acetate was 55.1% and the selectivity of thereof was 59.3% (onthe basis of the raw material of dichloroacetoxypropane).

EXAMPLE 12

Reaction was performed in the same manner as in Example 11 except thatthe allyl alcohol/dichloroacetoxypropane mole ratio was 1.0. From theresults of the gas chlomatographic analysis of the reaction liquid afterthe reaction for 3 hours, it was found that the conversion ofdichloroacetoxypropane was 84.1%, the yield of dichloropropanol was82.5% and the selectivity of thereof was 98.1% (on the basis of the rawmaterial of dichloroacetoxypropane).

EXAMPLE 13

Reaction was performed in the same manner as in Example 12 except thatconcentrated sulfuric acid was used as the catalyst.

From the results of the gas chlomatographic analysis of the reactionliquid after the reaction for 3 hours, it was found that the conversionof dichloroacetoxypropane was 83.5%, the yield of dichloropropanol was81.9% and the selectivity of thereof was 98.1% (on the basis of the rawmaterial of dichloroacetoxypropane).

EXAMPLE 14

Production of dichloropropanol: Production of dichloropropanol byalcoholysis of dichloroacetoxypropane with anhydrous allyl alcohol

Alcoholysis was effected as follows at an anhydrous allylalcohol/dichloroacetoxypropane mole ratio of 1.0.

40.0 g of dichloroacetoxypropane produced in Example 5, 13.6 g ofanhydrous allyl alcohol and 15 ml of a particulate cation exchange resinof particle sizes of 0.42 to 0.57 mm (Amberlite (trademark) IR-118 (H)type) were charged into a glass flask equipped with a Dimroth condenser,heated to 80° C. while stirring, and reacted for 3 hours. From theresults of the gas chlomatographic analysis of the reaction liquid, itwas found that the reaction liquid contained 12.3 g of unreacteddichloroacetoxypropane, 20.6 g of produced dichloropropanol, 16.0 g ofproduced allyl acetate and 3.9 g of unreacted allyl alcohol. Since thereaction system contained no water, no production of acetic acid wasfound. From the results, it was found that the conversion ofdichloroacetoxypropane was 69.3%, the yield. of dichloropropanol was68.3% and the selectivity of thereof was 98.7% (on the basis of the rawmaterial of dichloroacetoxypropane), and the yield of allyl acetate was68.2% and the selectivity of thereof was 98.6% (on the basis of the rawmaterial of dichloroacetoxypropane).

EXAMPLE 15

Production of dichloropropanol: Production of dichloropropanol bycontinuous alcoholysis of dichloroacetoxypropane with 70 wt % aqueousallyl alcohol solution

Continuous alcoholysis with a fixed bed reaction vessel was effected asfollows at an allyl alcohol/dichloroacetoxypropane mole ratio of 1.0.

10 ml of a particulate cation exchange resin (Amberlite (trademark)IR-118 (H) type) was filled in an upright glass tubing reaction vesselhaving an inner diameter of 14 mm, a length of 15 cm and a volume ofabout 18 ml and equipped with a side tubing at the upper portion, andthe reaction vessel was heated to 85° C. with an oil bath, while settingthe reaction vessel so that the outlet of the reaction vessel wasoutside of the oil bath. 3.27 g of 70 wt % aqueous allyl alcoholsolution and 6.73 g of dichloroacetoxypropane, per hour, were introducedinto the reaction vessel from the upper side tubing by metering pumps. Apolytetrafluoroethylene tube was connected with the outlet of thereaction vessel and the reaction liquid flowing out was introduced intoa flask of a recepter. The end portion of the polytetrafluoroethylenetube was set at the same level as the liquid level in the reactionvessel to keep the liquid level in the reaction vessel constant.

The reaction liquid in the receptor was analyzed, by gas chromatography,every hour. The weight of the liquid flowing out was 9.96 g per hour atthe stationary state, and the flowing out liquid had a composition of1.36 g of unreacted dichloroacetoxypropane and 3.76 g of produceddichloropropanol. From the results, it was found that the conversion ofdichloroacetoxypropane was 84.3%, the yield of dichloropropanol was74.1% and the selectivity of thereof was 92.8% (on the basis of the rawmaterial of dichloroacetoxypropane).

EXAMPLE 16

Production of dichloropropanol: Distillation of reaction liquid obtainedby alcoholysis with 70 wt % aqueous allyl alcohol solution

A reaction liquid obtained by scaling up the procedure of Example 15 wasdistilled as follows.

300 g of a reaction liquid obtained by scaling up the procedure ofExample 15 was charged in a 500 ml three-necked flask equipped with adropping amount-controlling cock and a fractionating column having areflux condenser and subjected to vacuum distillation under full refluxconditions. The distillation was continued while taking out a lowboiling point component from the top of the fractionating column under areduced pressure of 2.4 to 22 kPa until the low boiling point componentceased to distill.

The low boiling point component and a high boiling point component (theliquid retained in the flask) were analyzed by gas chromatography andusing a Karl Fischer moisture meter. It was found that the low boilingpoint component mainly contained allyl acetate, allyl alcohol, water andacetic acid and contained a slight amount of dichloropropanol anddichloroacetoxypropane.

The liquid retained in the flask mainly contained dichloropropanol andunreacted dichloroacetoxypropane, the total amount of which comprised99.5 wt % of the liquid retained in the flask.

EXAMPLE 17

Production of dichloropropanol: Production of dichloropropanol byalcoholysis with unhydrous allyl alcohol and separation ofdichloropropanol.

A reaction liquid was obtained by scaling up the procedure of Example14, the cation exchange resin of the catalyst was filtered off, anddichloropropanol was separated from the reaction liquid as follows.

2,000 g of a reaction liquid obtained by scaling up the procedure ofExample 14 was treated in the same manner as in Example 16 using anapparatus similar to that used in Example 16, and a low boiling pointcomponent was taken out from the top of the fractionating column. Thelow boiling point component was a homogeneous solution in an amount of726.0 g, and the retained liquid (high boiling point component) amountedto 1,233.4 g. The recovery was 98.0%.

When both components were analyzed by gas chromatography, it was foundthat the low boiling point component contained allyl acetate andunreacted allyl alcohol with a trace of dichloropropanol, while theretained liquid (high boiling point component) containeddichloropropanol and unreacted dichloroacetoxypropane with a trace ofallyl acetate.

684.0 g of the low boiling point component obtained was subjected todistillation under normal pressure using an Oldershow distillationcolumn. The low boiling point component from the top of the column was240.1 g of an azeotropic component of allyl acetate and allyl alcohol,which was then recycled to the second step (step to producedichloropropanol). The retained liquid of the low boiling pointcomponent was 436.0 g of allyl acetate, which was then recycled to thefirst step (step to produce dichloroacetoxypropane). The recovery was98.8%.

Further, 1,110.0 g of the retained liquid of the high boiling pointcomponent was subjected to distillation using an Oldershow distillationcolumn under a reduced pressure of 13.3 kPa. The liquid taken out was687.5 g of dichloropropanol containing a trace of allyl acetate, whichwas then introduced to the third step (step to produce epichlorohydrin).The liquid retained was 410.0 g of unreacted dichloroacetoxypropane,which was then recycled to the first step (step to producedichloroacetoxypropane). The recovery was 98.9%.

EXAMPLE 18

Production of epichlorohydrin

The following dehydrochlorination column was used for performingdehydrochlorination reaction of dichloropropanol and for stripping toimmediately separate epichlorohydrin produced from the reaction liquid.

The dehydrochlorination column body was made of glass and had an innerdiameter of 55 mmφ and a height of 1,500 mm. 10 porous plates eachhaving 280 holes of 1 mm diameter were disposed at an interval of 100 mmand each porous plate had a 5 mm-depth downcomer. Under the lowestplate, a nozzle for blowing steam was provided and a constant amount ofsteam could be fed through a flowmeter. Above the uppermost plate,liquid feed nozzles were provided for feeding dichloropropanol and anaqueous alkali solution. A dichloropropanol solution and an aqueousalkali solution were supplied by metering pumps and mixed immediatelybefore the liquid feed nozzle. From the top, a distillate was collectedthrough a condenser. At the bottom, a 500 ml round bottom flask wasfixed and a constant amount of solution was extracted by a metering pumpto give a bottom solution in an amount of 40 ml.

Using the above-described apparatus, dichloropropanol obtained by thealcoholysis described in Example 17 and a 9.5 wt % aqueous Ca(OH)₂slurry were supplied through the liquid feed nozzles at a rate of 83 g/hand 323 g/h, respectively, and at the same time, steam was blown throughthe steam blowing nozzle. The dichloropropanol concentration duringfeeding was 20 wt %. While extracting the waste from the bottom, theoperation was continued for about 2 hours to stabilize the reactionsystem. One hour later, the top distillate and the bottom liquid weresampled and the compositions thereof were analyzed. The dichloropropanolconversion was 90.1% and epichlorohydrin selectivity was 98.0%. Thetemperature at the middle of the column was 99° C.

EXAMPLE 19

Production of epichlorohydrin

Reaction was performed in the same manner as in Example 18 except forusing dichloropropanol obtained as described in Example 9. Thus, it wasfound that the conversion of dichloropropanol was 90.8% and theselectivity of epichlorohydrin was 97.7%.

What is claimed is:
 1. A process for producing dichloroacetoxypropane,comprising reacting allyl acetate with chlorine in a gaseous phase inthe absence of a catalyst.
 2. A process for producingdichloroacetoxypropane, comprising reacting allyl acetate with chlorinein a gaseous phase in the presence of a catalyst comprising an elementof Group 16 of the long-form Periodic Table, wherein the element ofGroup 16 is tellurium (Te).
 3. A process according to claim 1 or 2,wherein a diluent is added during the reaction of allyl acetate withchlorine.
 4. A process according to claim 1 or 2, wherein the reactionof allyl acetate with chlorine is carried out at a temperature of 70 to300° C.
 5. A process according to claim 1 or 2, wherein the reaction ofallyl acetate with chlorine is carried out under a pressure of 10 to1,000 kPa.
 6. A process according to claim 1 or 2, wherein the reactionof allyl acetate with chlorine is carried out at a temperature of 70 to300° C. and under a pressure of 10 to 1,000 kPa.
 7. A process accordingto claim 1 or 2, wherein the reaction of allyl acetate with chlorine iscarried out at a molar ratio of chlorine to allyl acetate ranging from0.001 to 1.5.
 8. A process according to claim 2, wherein the element ofGroup 16 of the long-form Periodic Table is in the form of a halide oran oxide.
 9. A process according to claim 2, wherein the catalyst is asupported catalyst.
 10. A process according to claim 2, wherein thecatalyst is used blended with a filler.
 11. A process for producingdichloropropanol comprising: a first step of reacting allyl acetate withchlorine in a gaseous phase in the presence of a catalyst comprising anelement of Group 16 of the long-form Periodic Table or in the absence ofa catalyst to produce dichloroacetoxypropane; and a second step ofsubjecting dichloroacetoxypropane obtained at the first step tohydrolysis or alcoholysis to produce dichloropropanol, wherein theelement of Group 16 is tellurium (Te).
 12. A process according to claim11, wherein allyl alcohol is used for the alcoholysis.
 13. A process forproducing epichlorohydrin comprising: a first step of reacting allylacetate with chlorine in a gaseous phase in the presence of a catalystcomprising an element of Group 16 of the long-form Periodic Table or inthe absence of a catalyst to produce dichloroacetoxypropane; a secondstep of subjecting dichloroacetoxypropane obtained at the first step tohydrolysis or alcoholysis to produce dichloropropanol; and a third stepof dehydrochlorinating dichloropropanol obtained at the second step toproduce epichlorohydrin, wherein the element of Group 16 is tellurium(Te).
 14. A process according to claim 13, wherein allyl alcohol is usedfor the alcoholysis.